Alkyl-1-mercapto substituted-2-benzimidazole-carbamates

ABSTRACT

ALKYL-1-MERCAPTO SUBSITUTED - 2 - BENZIMIDAZOLECARBAMATES OF THE FORMULA BELOW ARE USEFUL AS MITE OVICIDES AND FUNGICIDES.   1-(Z-S-),2-(R-OOC-NH-)BENZIMIDAZOLE   WHERE R IS METHYL, ETHYL, ISOPROPYL AS SEC-BUTYL; AND Z IS ALKYL OF 1 THROUGH 3 CARBON ATOMS, BENZYL OR DERIVATIVES THEROF AS DEFINED HEREINAFTER. AN EXEMPLARY SPECIES OF THIS GENERAL CLASS IS THE COMPOUND: METHYL - 1 (TRICHLOROMETHYLTHIO) - 2 - BENZIMIDAZOLECARBAMATE.

United States Patent Office 3,632,601 Patented Jan. 4, 1972 3,632,601ALKYL-l-MERCAPIO SUBSTITUTED-2- BENZlMIDAZOLE-CARBAMATES Hein L.Klopping, Wilmington, Del., assignor to E. I. du Pont de Nemours andCompany, Wilmington, Del. No Drawing. Application Mar. 20, 1968, Ser.No. 714,462,

now Patent No. 3,541,213, which is a continuation-inpart of applicationSer. No. 629,900, Apr. 11, 1967, which in turn is a continuation-in-partof application Ser. No. 548,034, May 6, 1966. Divided and thisapplication June 20, 1970, Ser. No. 56,645

Int. Cl. C07d 49/38 US. Cl. 260309.2 6 Claims ABSTRACT OF THE DISCLOSUREAlkyl-l-mercapto substituted 2 benzimidazolecarbamates of the formulabelow are useful as mite ovicides and fungicides.

N ll NH0 0 R i s Z where R is methyl, ethyl, isopropyl as sec-butyl; andZ is alkyl of 1 through 3 carbon atoms, benzyl or derivatives thereof asdefined hereinafter.

An exemplary species of this general class is the compound:

methyl 1 (trichloromethylthio) 2 benzimidazolecarbamate.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisionalof my copending application Ser. No. 714,462, filed Mar. 20', 1968, nowUS. Pat. 3,514,213, which application was a continuation-inpart of mythen copending application Ser. No. 629,900, filed Apr. 11, 1967, nowabandoned, which application was a continuation-in-part of my thencopending appli cation Ser. No. 548,034, filed May 6, 1966, nowabandoned.

BACKGROUND OF THE INVENTION This invention relates to mercaptosubstituted-2-benzimidazolecarbamates and to methods of using thesecompounds to prevent or mitigate damage to plants and inanimate organicmaterials by fungi and mites.

The survival of man has for a long time been dependent in a largemeasure upon his ability to protect from the various agents ofdestruction, plants and their products which satisfy his basic needs.With the rapidly increasing population of the world it becomesimperative that there be continuing great improvements in the efficiencyof the materials and the methods employed to provide this protection.These improvements can be in the form of effective control of more kindsof pests or in the form of requiring less material or work. Thematerials and methods of this invention represent marked advances inboth of these possible areas of improvement, as will be explained morefully.

I have discovered that application of the compounds of this invention bythe methods of this invention, surprisingly, entirely precludes orreduces damage to plants and inanimate organic materials due to bothfungi and mites. Fungus mycelia are killed or prevented from developingfurther by the presence of one or more of the compounds, i.e., thecompounds are fungicidal or fungistatic. The compounds further preventmite populations from expandingor reduce them to a low level or eveneliminate them by preventing the normal hatching of their eggs, i.e.,the compounds are mite ovicides.

The compounds and methods of this invention also make possible thecontrol of damage by both fungi and mites with an amazingly small amountof chemical and with surprisingly little effort. These advantages aredue in large measure to the fact that the compounds when properlyapplied, can enter and move about in plants. This means that an entireplant can be protected from mites and fungi with a simple application ofthe chemical to only a part of it, i.e., the compounds are systemic.Further, if the compounds are applied after a disease causing fungus isalready established within a plant, they can enter the tissues anderadicate the infection, i.e., the compounds are curative. Thus, theneed for applications prior to the actual incidence of the disease iseliminated under many circumstances.

SUMMARY OF THE INVENTION It has been found that the above outstandingfungicidal and mite ovicidal activity can be obtained by applying to thelocus of mite or fungus infestation, the compounds represented by thefollowing formulas:

Formula I N o O NH%OR wherein Formula IA wherein R is methyl, ethyl orisopropyl; and Z is trichloromethyl or 2,4-dinitrophenyl.

Most preferred within Formula I are the following compounds:

methyl-l-(trichloromethylthio)-2-benzimidazo1ecarbamate,

ethyl- 1 (trichloromethylthio -2-benzimidazolecarbamate,

methyl-1-(2,4-dinitrophenylthio)-2-benzimidazolecarbamate,

ethyl- 1- 2,4-dinitrophenylthio -2-benzimidazolecarbamate.

It will be understood that the compounds of this invention may exist intwo tautomeric forms 3 DETAILED DESCRIPTION OF THE INVENTION Thecompounds of Formula I can be prepared by reacting abenzimidazole-Z-carbamate with a sulfenyl chloride as shown in reactionschemes (1) and (2) below:

EXAMPLE 1 To a mixture of 19 parts of methyl 2-benzimidazolecarbamate,100 parts of chloroform, 9 parts of sodium bicarbonate and 10 parts ofwater, a total of 19 parts of trichloromethanesulfenyl chloride is addedgradually with stirring. The reaction is maintained at room temperaturewith external cooling. The entire reaction is stirred for an additionalhour at room temperature. The solid formed is removed by filtration,washed with two volumes of water and allowed to dry. This materialamounts to 27 parts of essentially pure methyl-l-(trichloromethylthio-2-benzimidazolecarbamate.

By using equivalent amounts of property substituted sulfenyl chloridesfor the trichloromethanesulfenyl chloride and equivalent amounts ofproperly substituted monoor disubstituted 2-aminobenzimidazoles for themethyl-Z-benzimidazole-carbamate, the following com pounds can besimilarly made:

isopropyl-l (o-nitrophenylthio -2-benzimidazolecarbamateisopropyl-1-(2,4-dinitrophenylthio) -2-benzimidazolecarbamateethyl-1-(trichloromethylthio)-2-benzimidazolecarbamateisopropyl-1-(trichloromethylthio)-2-benzimidazolecarbamate sec-butyl- 1-trichloromethylthio) -2-benzimidazole carbamate methyll-2,2,2-trifiuoroethylthio -2-benzimidazolecarbamatemethyl-1-(2-chloroethylthio)-2-benzimidazolecarbamate methyl- 1benzylthio -2-benzimid azolecarbamatemethyl-1-(m-trifluoromethylphenyl)-2-benzimidazolecarbamate ethyll-(pentafluoroethylthio -2-benzimidazolecarbamate ethyll-2-fluoroethylthio -2-benzimidazolecarb amate EXAMPLE 2 A total of 20parts of 2,4-dinitrophenylsulfenyl chloride is added gradually to astirring mixture composed of 19 parts of methyl2-benzimidazolecarbamate, parts of chloroform, and 8 parts of pyridine.The reaction is stirred for an additional hour at room temperature uponcompleting the addition of the 2,4-dinitrophenylsulfenyl chloride. Atthis point, the solvent is removed under reduced pressure and theresidue is washed with water and dried. The remaining solid isessentially pure methyl-1-(2,4dinitrophenylthio)-2-benzimidaz0lecarbamate.

By using equivalent amounts of properly substituted sulfenyl chloridesfor the 2,4-dinitrophenyl sulfenyl chloride and equivalent amounts ofproperly substituted monoor di-substituted Z-aminobenzimidazoles for themethyl 2- benzimidazolecarbamate, the following compounds can besimilarly made:

methyl-1-(2,4-dichlorophenylthio)-2-benzimidazolecarbamatemethyl-1-(p-fiuorophenylthio--2-benzimidazolecarbamatemethyl-1-(2,4-dimethylphenylthio)-2-benzimidalolecarbamatemethyl-1-(2,4-dinitrophenylthio) -2-benzimidazolecarb amatemethyl-1-(phenylthio)-2-benzimidazolecarbamate sec-butyl- 1-(o-methylphenylthio -2-benzimidazolecarb amatemethyl-1-(3,4-dimethylphenylthio)-2-benzimidazolecarb amatemethyl-1-(o-nitrophenylthio)-2-benzimidazolecarbamate methyl-1(p-nitrophenylthio -2-benzirrfidazolecarbam ate methyl- 1- 3,4-dichlorophenylthio -2-benzimidazolecarb amate methyl- 1 (benzylthio)-2-benzimidazolecarbamate methyl- 1 (o-methylbenzylthio-2-benzimidazolecarbamate, methyl- 1- (o-nitrobenzylthio-2-benzimidazolecarb amatemethyl-1-(p-chlorobenzylthio)-2-benzimidazolecarbamate As mentionedpreviously, it has been found that the compounds of this inventionpossess outstanding fungicidal and mite ovicidal activity when employedto prevent or mitigate damage to plants and inanimate organic materials.A further aspect of this invention involves methods which when used inconjunction with the compounds of this invention, result in advances inmite and fungus control of great practical importance. A furtheradvantage of the compounds of the invention is that they have a loworder of mammalian toxicity. The paragraphs which follow describe inmore detail the utility of this invention.

The compounds of the invention control a wide variety of fungus diseasesof foliage, fruit, stems and roots of growing plants without damage tothe host. Fruits, tubers, bulbs, roots, seeds and other plant partsharvested for food, animal feed or for other purposes are protected fromfungus deterioration during processing, distribution and storage. Seeds,tubers, cuttings and other plant propagation materials are protectedfrom fungus attack during handling and storage, as well as in the soilafter planting. Wood, fabric, fiber board, paper and other industrialmaterials are protected from unsightly stain and destructive decaycaused by fungi. Luggage, shoes, shower curtains, carpets, mats,clothing and other useful household, public or industrial items areprotected from rot, fungus stains and mold growth.

The many fungi against which the compounds of this invention are activemay be represented by, but is not intended to be limited to, thefollowing: Venturia inaequalis, which causes apple scab; Podosphaeraleucotricha, which causes powdery mildew on apple; Uromyces phaseoli,which causes bean rust; Cercospora apii, which causes early blight ofcelery; Cercospora beticola, which causes leaf spot of sugar beets;Sclerotinia sclerotiorum, which causes rot of vegetable crops, such aslettuce, beans, carrots, and celery; Coelltotrichum spp., which causeanthracnose of fruits and vegetables, such as beans, tomatoes andcoffee; Septoriw apii, which causes late blight of celery; Cercosporamusae, which causes Sigotoka disease of banana; Piricularia sp., whichcauses Johnson spot on banana; Erysiphe cichoracaerum, which causespowdery mildew on cantaloupe and other cucurbit crops; Penicilliumdigitatum, Phomopsis spp., and Diplodia natalensis, which cause fruitrots on citrus; Ceratostomella ulmi, which causes Dutch elm disease;Sphaerotheca humuli, which causes powdery mildew on roses; Diplocarpanrosae, which causes black spot on roses; Ramu laria sp., which causesleaf spots on ornamental plants; Botrytis cinerea, which causes blossomand fruit rots of ornamentals, fruits and vegetables; Uncinula necator,which causes powdery mildew on grapes; Guignardia bidwellii which causesgrape black rot; Melonconium fuligineum, which causes white rot ofgrapes; Coccomyces hiemalis, which causes cherry leaf spot; Cytosporasp., which cause cankers of trees; Cladosporium carpophilum, whichcauses peach scab; Fusicladium efiusum, which causes pecan scab;Erysiphe graminis, which causes powdery mildew on cereals; Monolinz'a(Sclerotinia) laxa and M. fructicola, which cause brown rot of stonefruits, such as peaches, cherries and apricots; Pseudopeziza ribes,which causes leaf spot on gooseberry; Piricularia oryzae, which causesrice blast; Puccinia recondita, P. coronata and P. glumarum, which causeleaf rusts of wheat, oats and grasses, respectively; Puccinia graministritici, which causes stem rust of wheat; Claviceps purprea, whichcauses ergot of rye and grasses; Aspergillus niger, which causes cottonboll rot as well as decay following wounding in many plant tissues;Aspergillus flavus, which causes mold growth on peanuts, as well as onother food and feed materials; Aspergillus terreus, which is common insoil and attacks vegetable matter; Tilletia caries and other Tilletiaspecies, which cause common bunt of wheat; Ustilago tritz'ci, Ustilagonigm, Ustilago avena (and other Ustilago species), which cause loosesmut of Wheat, barley, and oats, respectively; Urocystis tritici andother Urocystis species, which cause loose smut of wheat; Sphacelothecasorghi, which causes covered smut of sorghum; Ustilago hordei andUstilago kolleri, which cause covered smut of barley and oats,respectively; Pithomyces chartorum, which is present in turf, pastures,and other grassy areas and is known to have several secondary effects;Gloeodes pomigena, which causes sooty blotch on apples; Physalosporaobtusa, which causes black rot on apples; Microthyriella rubz', whichcauses flyspeck on apples; various species of Rhizoctonia, Fusarium andVerticillium present in soil and attacking the roots or otherunderground parts and the vascular system of a variety of plants;various species of Penicillium growing on such things as fabric, fiberboard, leather goods and paint; species of Myrothecium attacking suchitems as shower curtains, carpets, mats and clothing.

The mite ovicidal action of the compounds of this invention is useful inpreventing the development of damaging populations of mites or incausing the gradual reduction of existing populations. The movement ofmites is limited. Thus, an increase in population or the continuation ofa high population in a particular locus depends largely upon thehatching of eggs laid in that locus.

Mite eggs do not hatch to produce living young if these eggs are treatedwith one of these compounds, or if they are laid on a surface containingone of these compounds. Further, the eggs will not hatch if they arelaid by a female mite that has been in contact with one of thesecompounds, or are laid by a female mite that is ingesting or hasrecently ingested food such as plant juices containing one of thesecompounds. This interference with the hatching of eggs prevents thepopulation from increasing significantly beyond that present at the timeof treatment. Also, this ovicidal action, along with the high naturalmortality of adults, can largely eliminate mites from an alreadyinfested area over a relatively short period of time. Further, as longas the compounds are present on the surface the mites occupy or remainin their food supply, new populations cannot develop.

Many species of mites which cause damage to fruits, field crops,vegetables, and ornamentals under a wide variety of circumstances, arecontrolled by the compounds and methods of this invention. The extent ofthe practical utility of the mite control obtained is represented by,but is not intended to be limited to, the following listing of specificsusceptible mites along with the types of damage that they can cause:Panonychus ulmi (European red mite) and Tetranychus telarius(two-spotted mite) which are commonly called orchard mites; these mitesattack a great many deciduous tree fruits including apples, pears,cherries, plums and peaches; Tetranychus atlanticus (Atlantic orstrawberry mite), T. cinnabarinus (carmine spider mite) and T. pacificus(Pacific mite); these mites attack cotton and numerous other cropplants; Paraletranychus citri (citrus red mite) and others which attackcitrus; Phyllocoptruta alez'vora which causes citrus rust; Bryobiapraetiosa (clover mite) which attacks clover, alfalfa and other crops;Phyllocoptruta oleivora, the citrus rust mite; Acrez'a neocynodontiswhich attacks grasses and other plants; Tyrophagus lintneri which is aserious pest in stored foods and on cultivated mushrooms andLepidoglyphus destructor which injures Kentucky bluegrass seed instorage.

The compounds of this invention when applied by certain of the methodsof this invention enter and move freely within plants, i.e., they aresystemic. Thus both fungi and mites can be controlled in plants in partswell removed from the point of application. In view of this activity thecompounds can be applied to seeds; thus the treatment of cucumber seedswith a few grams per 50 kilograms of seed of a compound of thisinvention provides control of powdery mildew (Erysiphe cichoracearum)and spider mites such as Tetranychus urticae on the resulting plants forperiods in excess of 40 days. Application to soil also provides controlof certain foliage diseases and mites on plants growing in the treatedsoil. Spray or dust treatments of plant foliage and stems impartprotection against both fungi and mites to other parts of the plant notactually sprayed and to new foliage developing later.

There are important practical advantages associated with the use of aneffective systemic pesticide. Thus, successful application to seed asdescribed, results in great savings in chemical and application costs.Soil application which effectively protect entire plants for an extendedpe riod also represent similar savings. Distribution within the plantfollowing foliage treatment eliminates the need for frequent retreatmentto protect rapidly growing tissue. Also, materials within the plant arenot subject to removal by rainfall. Similarly, movement or translocationof the chemical within the plant can provide protection to those partsof the plant that may not have been covered by the original sprayapplication. This is of particular importance with plants of densegrowth character resisting the intrusion of the spray and also to tallplants, such as shade trees, where the spray will not reach to the top.

An additional valuable characteristic of the compounds of this inventionis their ability to prevent the spread or to kill fungus infectionalready established within a plant, i.e. they are curative. Thus, thecompounds need not be applied until after conditions develop whichpermit the actual initiation of fungus attack. This means that, undersome circumstances, it is possible to avoid applying any chemical duringthe entire life of the crop. In other cases,

only a part of the normal full schedule of pesticide is required.

Therefore great savings both in chemical cost and application labor arepossible with compounds capable of systemic and curative performance.Another saving is afforded by the compounds of this invention throughthe fact that both fungi and mites are controlled by applications of asingle chemical.

The compounds of this invention provide protection from damage caused byfungi, mites or both when applied to the proper locus by the methodsdescribed hereinafter and at a sufficient rate to exert the desiredfungicidal and mite ovicidal effect. They are especially suited for theprotection of living plants such as fruit-bearing trees, nut-bearingtrees, ornamental trees, forest trees, vegetable crops, horticulturalcrops (including ornamentals, small fruits and berries), fiber crops,grain and seed crops, sugarcane, sugar beets, pineapple, forage and haycrops, beans, peas, soybeans, peanuts, potatoes, sweetpotatoes, tobacco,hops, turf and pasture.

Living plants may be protected from fungi and mites by applying one ormore of the compounds of this invention to the soil in which they aregrowing or in which they may subsequently be seeded or planted; or toseeds, tubers, bulbs or other plant reproductive parts prior toplanting; as well as to foliage, stems and fruit of the living plant.Living plants can also be protected by dipping the root system orphysically injecting the chemical or chemicals into roots or stems.

Soil applications are made from dusts, granules, pellets, slurries orsolution. Preferred rates for application of the compounds of thisinvention to soil in which plants are or will be growing range from 0.01to 500 parts per million by weight of the soil in which the roots are orwill be growing. More preferred use rates are in the range of 0.1 to 50parts per million, and the most preferred rates are in the range of 0.25to 25 parts per million.

Preferred rates for application to seeds, tubers, bulbs or other plantreproductive parts, range from 0.03 to 6000 grams of active compound ofthis invention per 50 kilograms of planting material treated. Morepreferred rates are in the range of 0.3 to 3000 grams of active compoundper 50 kilograms. The most preferred rates are in the range of 2.8 to1500 grams per 50 kilograms.

Applications are made from dusts, slurries or solutions. Such treatmentsprotect the treated parts themselves from damage due to fungi, mites, orboth, and in addition, impart extended protection against both types ofpests to the resulting new plants.

Preferred rates for application of the compounds of this invention tofoliage, stems and fruit of living plants range from 0.012 to 60kilograms of active ingredient per hectare. More preferred rates are inthe range of 0.025 to 30 kilograms per hectare and the most preferredrates are in the range of 0.05 to 15 kilograms per hectare. The optimumamount within this range depends upon a number of variables which arewell known to those skilled 8 in .the art of plant protection. Thesevariables include, but are not limited to, the disease to be controlled,Weather conditions expected, the type of crop, stage of development ofthe crop, and the interval between applications. Applications within therange given may need to be repeated one or many more times at intervalsof l to 60 days. Applications are made from dusts, slurries orsolutions.

Preferred rates for dip applications to roots of living plants are inthe range of 0.5 to 18,000 grams of active ingredient per 380 liters ofWater or other liquid carrier. More preferred rates are in the range of4.5 to 9,000 grams per 380 liters and the most preferred rates are inthe range of to 4500 grams per 380 liters.

Preferred rates for injection into the roots or stems of living plantsare in the range of 0.01 to 10,000 parts per million of Water or otherliquid carrier. More preferred rates are in the range of 0.1 to 5,000parts per million. The most preferred rates are in the range of l to1,000 parts per million.

Plant parts such as fruits, tubers, bulbs, foliage roots and the like,harvested for food or feed, are protected from decay and otherdeterioration caused by fungi or mites during processing, distributionand storage by treatment with an active compound of this invention. Theplant parts to be so protected can be clipped in a liquid bathcontaining the active ingredient, dusted with a finely dividedpreparation of the active ingredient, sprayed, misted with an aerosolcontaining the compound, or enclosed in wrapping or packing materialsimpregnated with the active compound.

If a liquid bath is used, it can contain an amount of the activeingredient in the range of l to 5,000 parts per million of the weight ofthe fluid. A more preferred range for the bath is 5 to 2,500 parts permillion, and the most preferred range is 10 to 1,000 parts per million.

Dusts as Well as wrapping or packing materials used for this type ofapplication can contain 0.01 to 10% of the active ingredient. Morepreferred rates are in the range of 0.1 to 5% and the most preferredrates are in the range of 0.2 to 2.5%.

Damage by mites to stored organic products such as grain, seed, bulbs,tubers, meat or animal hides is kept to a minimum by treating thefloors, walls, portions, and other parts of warehouses or otherstructures with one or more of the active compounds. Applications aremade by the use of dusts, sprays, or aerosols with preferred use ratesin the range of 0.05 to 1000 grams of the active compound of thisinvention per 93 square meters of surface to be kept free of excessivemite populations.

As was previously set forth, the compounds of this invention areespecially suited for use on living plants. Application to the foliage,stems and fruit of plants at the rate indicated above is generallyaccomplished by employing sprays, dusts or aerosols containing theproper amount of active ingredient. For the control of mites and fungiwhich are regularly present, applications often start prior to the timethat the problem actually appears and continue on a pre-determinedschedule. Such a procedure is termed preventive or protective.

With the compounds of this invention, successful control of plantdiseases can also be accomplished by applications made after they arepresent. Fungus mycelia within the plant tissue are actually killed.This approach or effect is termed curative or eradicant and permits theuser to realize considerable savings.

Curative control of plant diseases with the compounds of this inventionis enhanced if the treated plant parts are moist for one or more periodsof 2 to 12 hours each soon after the active compound is applied. Oftenthe slow drying of an original spray treatment or naturally occurringrains, mists, fogs or dews will accomplish this. Under othercircumstances, such as during dry periods or in shelters such asgreenhouses, it is necessary to keep the plants moist by some specialeffort for best results.

When the compounds of this invention are applied, their activity can beenhanced by using certain adjuvants, for example in the water in whichthe benzimidazole fungicides are dispersed. These adjuvants may besurface active agents, oils, humectants, enzymes, carbohydrates, andorganic acids. They improve the performance on tubers, on foliage, intreatments used for dip application to roots of living plants, in thecase of liquids used for injection into the roots or stems of livingplants, or in mixtures used to treat fruits, tubers, bulbs, roots, andthe like, after harvest.

Surface active agents that enhance fungus control and mite control bythe compounds of this invention include sulfonated and sulfated aminesand amides, diphenyl sulfonate derivatives, ethoxylated alcohols,ethoxylated alkylphenols, ethoxylated fatty acids, ethoxylated fattyesters and oils, polyethylene oxide/ polypropylene oxide combinations,alkylsulfonates, fluorocarbon surfactants, glycerol esters, ethoxylatedalcohol sulfates, glycol esters, isethionates, sulfated ethoxylatedalkylphenols, lanolin derivatives, lecithin and lecithin derivatives,alkanol amides, phosphate derivatives, monoglycerides and derivatives,quaternaries, sorbitan and sorbitol derivatives, sulfosuccinates,alcohol sulfates, sulfated fatty esters, sulfated and sulfonated oilsand fatty acids, alkylbenzene sulfonates, imidazolines, taurates,ethoxylated mercaptans, ethoxylated amines and amides, modified phthalicglycerol alkyd resins, and similar materials. The oils includenonphytotoxic aliphatic spray oils and triglycerides, either with orwithout emulsifier to permit dispersion in water. Humectants such asglycerin or ethylene glycols, enzymes such as bromelin, andcarbohydrates such as glucose, lactose, and dextrose are also useful.Organic acids of interest include glycolic and gluconic acids. Althoughthe precise manner in which these additives improve the performance ofthe fungicides of this invention is not known, the effect is,nevertheless, startling, and it is possible that these additives improvethe penetration into the plant or translocation throughout the plant ofthe fungicides of this invention.

Preferred surface active agents to improve the fungicidal and miteovicidal activity of these compounds are products such as dioctyl sodiumsulfosuccinates (Aerosol OT and Aerosol OT-B), blends of aromaticsulfonates and ethylene oxide derivatives (AgrimuP GM, Agrimul A-100,Agrimul N-100, Emcol H50A, Emcol H53), polyoxyethylene sorbitololeate/laurate (Atlox 1045A), sodium lauryl sulfate (Duponol ME),polyoxyethylated vegetable oils (Emulphr EL719), lecithin derivatives(Emultex R), acidic complex organic phosphate esters (Gafac RE-610,Victawet), aliphatic amide alkyl sulfonates (Hyfoam Base LL), oleic acidesters of sodium isethionate (Igepon AP78), sodium N- methyl-N-oleoyltaurate (Igepon T77), sodium salt of sulfated lauryl and myristylcolamide (Intramine Y), polyethylene glycol 400 oleic acid esters(NonisoP 210), sodium dodecylbenzene sulfonates (Sul-Fon-Ate AA 10,Ultrawet K), polyoxyethylene ethers with longchain alcohols (Surfonic LR30, Alfonic 10126, Brij 30, Tergitol TMN), ethylene oxide condensateswith propylene oxide/ ethylene diamine condensates (Tetronic 504),polyhydric alcohol esters (Trem 014), modified phthalic glycerol alkydresins '(Triton B 1956), quaternaries (Zelec DP), alkylphenol ethyleneoxide condensates (Dowfax 9N4, Dowfax 9N10, Hyonic 9510, .Tergitols) andthe like. Examples given in parentheses are illustrative and do notexclude other unnamed commercial products. Examples of other surfaceactive agents in each of these several categories are listed inDetergents and Emulsifiers, 1965 Annual, or 1966 Annual, published byJohn W. McCutcheon Inc., 236 Mt. Kemble Ave., Morristown, N. J.

Preferred oils include spray oils such as Orchex 796 made emulsifiablewith Trition X-45, castor oil made emulsifiable with Trition X1l4, cornoil made emul- 10 sifiable with Triton X-114, Volck Oil #70, Sunoco OilNo. 7B and similar nonphytotoxic spray oils of vegetable, animal ormineral origin.

The preferred rates for these surfactants when used in sprays is in therange from 10 to 10,000 parts per million of the spray fluid. Morepreferred rates are in the range of 30 to 3,000 parts per million andthe most pre ferred rates are in the range of to 1,000 parts permillion.

For dusts, the preferred surfactant rates are in the range of 1,000 to300,000 parts per million of the material actually applied. Morepreferred rates are in the range of 5,000 to 200,000 parts per millionwith the most preferred rates being in the range of 10,000 to 100,000parts per million.

As previously mentioned, the compounds of the invention are systemic.For systemic applications to aboveground parts, such as foliage, stemsand fruit, the presence of a surface-active agent in the spray or dustenhances activity. Use rates for the surface active agent here are thesame as for sprays and dusts for preventive or curative control asdiscussed above. Systemic effect from the treatment of above-groundparts is also enhanced by moisture on the treated surfaces for one ormore periods of 2 to 12 hours each.

Systemic control of both mites and fungi on plants is also accomplishedby applications to seeds, tubers, bulbs or other reproductive partsprior to planting as Well as by application of the chemical to the soilin which the plants to be protected are, or will be, growing.Application to reproductive parts prior to planting is effected throughthe use of sprays, dips, dusts or aerosols containing one or more of thecompounds of this invention. Treatment of soil is accomplished byphysical mixing prior to planting, distribution in the furrow atplanting time, application in transplant water, placement in the soil ina band or sheet with specialized equipment, injection through irrigationwater or by distribution on the field surface.

The fungicidal and mite ovicidal compositions of the invention containin sufficient amount to exert fungicidal or mite ovicidal action, one ormore compounds of this invention in admixture with a carrier material orconditioning agent of the kind used and commonly referred to in the artas an adjuvant or modifier. The general classes of adjuvants applicableto the compounds of this invention are inert solids, organic liquidsolvents, organic liquid or aqueous diluents and surface-active agents.Formulations adapted for ready and eflicient application usingconventional applicator equipment are prepared by compounding thecompounds of this invention with suitable adjucants by mixing, grinding,stirring or other conventional processes. Normally the active ingredientcomposes 195% by weight of the fungicidal or mite ovicidal composition.

Solid compositions can be in the form of water-dispersible powders,dusts, pellets and granules. Water-dispersible powders are particularlyuseful and can be prepared by simple mixing and grinding steps and canbe either used as such, diluted with inert solids to form dusts orgranules, or suspended in a suitable liquid medium for spray or seedtreatment application. The powders usually comprise active ingredientadmixed with varying amounts of conditioning agents, surface-activeagents and stabilizers. The classes of extenders suitable for thewettable powders of this invention are clays such as the kaolins,diatomaceous earths, calcium carbonates, sulfur, sodium sulfate, andalso synthetic silicas and silicates. Diluents that have been surfacereacted, such as organic acid coated calcium carbonate, can also beused. Diluents of organic origin such as walnut shell flour, li-gninsulfonate, corn cob flour, or carbohydrates can also be used. Inaddition, natural or synthetic frangible resins can be used.

Among the preferred diluents are coated calcium carbonate, corn cobflour, starch, sucrose, sulfur, sodium sulfate and partiallydesulfonated sodium lignin sulfonate.

I l It is also preferred that the diluents be used in an anhydrousstate.

The active ingredient usually makes up from about 2590% of thesewettable powder compositions. These wettable powders can also beconverted to dusts containing 1-25% of active material by mixing orgrinding with one or more of the diluents listed above, or withpyrophyllite, volcanic ash and other dense, rapid-settling inert solids.Alternatively, dusts can be prepared by grinding the dust diluents withthe active ingredient, or by preparing dust concentrates for furtherdilution. These dust concentrates can contain from 80-95% of the activeingredient, blended and ground with diluents and, if desired, smallamounts of surface active agents.

For the granule compositions of this invention, the most suitablecarriers are of two types. The first are porous, absorptive, preformedgranules, such as preformed and screened granular clays, heat expandedgranular screened vermiculite, or granular botanicals. On any of these,a solution or aqueous or nonaqueous suspension of the active agent canbe sprayed at concentrations up to 25 weight percent of the totalweight. In addition to the active component, the solutions orsuspensions can contain surfactant and also binders such as sucrose orswollen starch to aid in adhering small particles of dispersed productto the dried granules. Such adhesive materials may also be surfactantsand include such products as polyvinyl alcohol, calcium and magnesiumlignin sulfonate in admixture with wood sugars, acrylate and asphaltemulsions, abietates, etc. Oils or other non-volatile liquids likeglycols can also be used to improve adhesion.

The second suitable type of carrier is the powdered kaolinitic clays, orbentonitic clays in the sodium, calcium or magnesium forms. These claysare blended with the active components and optionally surfactants togive mixtures that are granulated and dried to yield granular materialwith the active component distributed uniformly throughout the mass.Other suitable diluents for granulation are sulfur, organic dusts suchas corn cob flour, starch, dextrin, sucrose, in conjunction with bindersand surfactants. Such granules can also be made with 25 to 30 weightpercent active component, but more frequently a concentration of aboutweight percent is desired for optimum distribution. Similar compositionscan be made by extruding the mixture in the presence of moisture orother liquids such as polyethylene glycols and converting the extrusionsinto granules or pellets by a suitable combination of cutting, drying,and crushing steps. The granular compositions of this invention are mostuseful in a size range of -60 mesh (approx. 0.251.3 mm.).

Liquid compositions employing one or more of the active compounds ofthis invention are prepared by admixing the active ingredient with asuitable liquid diluent medium. The active ingredient can be either insolution or in suspension in the liquid medium. Typical of the liquidmedia which can be used are water, parafl inic spray oils, alkylatednaphthalenes, xylene, alcohols, chlorinated hydrocarbons and ketones.The active ingredient usually makes up from about 0.5 to 50% of theseliquid compositions. In addition, surface-active agents, particularlyemulsifiers, can be present to aid in the suspension or dispersion or toemulsify the composi tion into water.

Compositions of the invention, especially liquids and wettable powders,contain as a conditioning agent one or more surface-active agents inamounts sufficient to render a given composition readily dispersible inwater or in oil. By the term surface-active agent, it is understood thatwetting agents, dispersing agents, suspending agents and emulsifyingagents are included.

Suitable surface-active agents include anionic, cationic, and non-ionictypes. In general, less than 10% by weight of the surface-active agentis present in the compositions of this invention, although frequentlythe amount of 12 surface-active agent in these compositions is less than2% by weight.

Preferred wetting agents are alkylbenzeneand alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chainacid esters of sodium isethionate, esters of sodium sulfosuccinate,sulfated or sulfonated fatty acid esters, petroleum sulfonates,sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferreddispersants are methyl cellulose, polyvinyl alcohol, sodium, calcium,and magnesium lignin sulfonates, polymeric alkylnaphthalene sulfonates,sodium naphthalene sulfonate, polyvinylpyrrolidone derivatives,polymethylene bisnaphthalenesulfonate and sodium N-methyl-N-(long chainacid taurates.

Wetting and dispersing agents in these preferred wettable powdercompositions of this invention are usually present at concentrations offrom about 0.5 weight percent to 5 weight percent. The inert extenderthen completes the formulation. Where needed, 0.1 weight percent to 1.0weight percent of the extender can be replaced by a corrosion inhibitoror an antifoaming agent, or both. In some instances, it may beadvantageous to use larger amounts of dispersants such as the ligninsulfonates in wettable powder, pellet, granule and dust compositions. Insuch a case, the lignin sulfonates additionally act as diluents forpowders and as binder for granules and pellets.

Emulsifying agents most suitable for the liquid compositions of thisinvention are alkylaryl polyethoxy alcohols, condensation products ofethylene oxide with long-chain alkyl alcohols, mercaptans or amines,sorbitan fatty acid esters, polyethylene glycol fatty esters, fattyalkylol amide condensates, amine salts of fatty alcohol sulfates, andoil soluble salts of petroleum sulfonates. Mixtures of emulsifyingagents are often preferred. Such emulsifying agents will comprise fromabout 3 to 10 weight percent of the total composition. As describedabove, however, much greater amounts of emulsifying agent can be used togive improved results.

The compounds of this invention and the oils, humectants, enzymes,carbohydrates, and acids useful to enhance the fungicidal andmite-ovicidal activity of these compounds can be brought together inseveral ways. For example, the additive which will enhance activity canbe mixed with compounds of the invention when spray slurriesare beingprepared. It is often also possible and conventent to produceformulations in which the additive and the compound of the inventionwill both be present in the composition, which is then convenient toapply. Such compositions can be powders, granules, suspensions, or evensolutions, depending upon the physical and chemical characteristics ofthe components that are to be prepared. It will be readily understood bythose skilled in the trade and in the light of the above teachings thatthe ratios of active ingredients compound to additives may vary widely.Thus, the additive may be present in such mixtures within the range offrom 33 to 10,000 parts per parts of the compounds of this invention.More preferred are rates of from 40 to 5,000 parts of additives per 100parts of active ingredients and a range of ratios from 50 to 3,500 per100 parts of compound is even more preferred.

Among non-ionic and anionic surfactants, those most suitable for thepreparation of the dry, wettable products of this invention are solidforms of compounds known to the art as wetters and dispersants.Occasionally a liquid, non-ionic compounds classified primarily as anemulsifier can serve as both wetter and dispersant.

Such compositions can contain, in addition to the active ingredients ofthis invention, conventional insecticides, miticides, bactericides,nematocides, fungicides, or other agricultural chemicals such as fruitset agents, fruit thinning compounds, fertilizer ingredients and thelike, so that the compositions can serve useful purposes in addition tothe control of fungi and mite infestations.

13 The following are illustrative of the agricultural chemicals that canbe included in the compositions or, additionally, that may be added tosprays containing one or more of the active compounds.

1,2,3,4,l0,10-hexachloro-1,4,4a,5,8,8a-hexahydro-L4-endo-exo-5,S-dimethanonaphthalene (aldrin);

1,2,3,4,5,6-hexachlorocyclohexane (lindane);

2,3,4,5,6,7,8,8-octachloro-4,7-methano-3a-4,7,7a-tetrahydroindane;

l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a-5,6,7,8,8a-

octahydro-l,4-endo-cxo-5,S-dimethanonaphthalene (dieldrin);

1,2,3,4,10,l-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-

octahydro-l,4-endo-endo-5,6-dimethanonaphthalene '(endrin);

1 (or 3a), 4,5,6,6,8,8-heptachloro-3a-4,7,7a-tetrahydro-4,7-methanoindene;

1,1,l-trichloro-2,2-bis(p-methoxyphenyl) ethane (methoxychlor) 1,l-dichloro-2,2-bis (p-chlorophenyl) ethane;

chlorinated camphene having a chlorine content of 2-nitro-1, l-bisp-chlorophenyl butane;

1-naphthyl-N-methylcarbamate (carbaryl);

methylcarbamic acid, ester with phenyl, 4-(dimethylamino)-3,5-dimethyl;

methylcarbamic acid, ester with 1,3-dithiolan-2-one oxime;

0,0-diethyl-O-(2-isopropyl-4-methylpyrimid-6-yl) thiophosphate;

0,0-dimethyl-1-hydroxy-2,2,2-trichloroethyl phosphonate (diazinon);

0,0-dimethyl-S-( 1,Z-dicarbethoxyethyl)dithiophosphate (malathion)0,0-dimethyl-O-p-nitrophenyl thiophosphate (methyl parathion);

0,0-dimethyl-O- 3-chloro-4-nitrophenyl) thiophosphate;

0,0-diethyl-O-p-nitrophenyl thiophosphate (parathion);

di-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclopentenl-onechrysanthemumate;

0,0-dimethyl-O-(2,2-dichlorovinyl)phosphate (dichlorovos) mixturecontaining 53.3% Bulan, 26.7% Prolan and 20.0% related compounds;

0,0-dimethyl-0-(2,4,5-trichloropheny1)phosphorothioate;

0,0-dimethyl-S- 4-oxo-l ,2,3-benzotriazine-3 (4H) -ylmethyl)-phosphorodithioate (azinphosmethyl);

bis (dimethylamino)phosphonous anhydride;

0,0-diethyl-O-(2-keto-4-methyl-7-a-pyranyl)thiophosphate;

0,0-diethyl (S-ethyl mercaptomethyl)dithiophosphate;

calcium arsenate;

sodium aluminofluoride;

dibasic lead arsenate;

-chloroethy1-1-methyl-2-(p-tert-butylphenoxy)ethyl azobenzene;

ethyl 2-hydroxy-2,2-bis(4-chlorophenyl)acetate;

0,0-diethyl-O-(2-ethylmercapto)-ethyl)thiophosphate (demeton);

2,4-dinitro-6-sec-butyl phenol;

toxaphene;

O-ethyl-O-p-nitrophenylbenzenethiophosphonate (EPN);

4-chlorophenyl-4-chlorobenzene sulfonate;

p-chlorophenyl-phenyl sulfone;

tetraethyl pyrophosphate (TEPP);

1, l-bis (p-chlorophenyl) ethanol;

1,1-bis(chlorophenyl) -2,2,2-trichloroethanol (dicofol)p-chlorophenyl-p-chlorobenzyl sulfide;

bis(p-chlorophenoxy)methane;

3-(1-methyl-2-pyrrolidyl) pyridine;

mixed ester of pyrethrolone and cinerolone keto-alcohols and twochrysanthemum acids;

cube and derris, both whole root and powdered;

ryanodine;

mixture of alkaloids known as veratrine;

methyl-Z-(o-hydroxyphenyl)-l,3-dithiolane carbamate;

methyl-2-(o-hydroxylphenyl)-l,3-dioxolane carbamate;

dl-2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one esterified with amixture of cis and trans dl-chrysanthemum monocarboxylic acids;

butoxypolypropylene glycol;

ethyl 2-hydroxy-2,2-bis(4-chlorophenyl)acetate (chlorobenzilate)p-dichlorobenzene;

2-butoxy-2'-thiocyanodiethyl ether;

naphthalene;

methyl O-carbamylthiolacetohydroxamate;

1,1-dichloro-2,2-bis (p-ethylphenyl) ethane;

methyl O-(methylcarbamoyl)thiolacetohydroxamate (methomyl);

S-methyl 1-dimethylcarbamoyl-N-[ (methylcarbamoyl) oxy]thioformimidate;

p-dimethylaminobenzenediazo sodium sulfonate;

Z-heptadecylimidazoline acetate (glyodin);

quinone oxyaminobenzooxohydrazone;

tetraalkyl thiuram disulfides such as tetramethyl thiuram disulfide ortetraaethyl thiuram disulfide;

metal salts of ethylene bisdithiocarbamic acid, e.g.

manganese, zinc, iron and sodium salts;

pentachloronitrobenzene;

2- l-methylheptyl)-4,6-dinitrophenyl crotonate and other nitrophenolderivatives;

N-dodecylguanidine acetate (dodine);

N- (trichloro methylthio phthalimide;

N-trichloromethylthiotetrahydrophthalimide (captan);

cis-N-[1,l,2,2-tetrachloro ethyl)thio]-4-cyclohexene- 1,2-dicarboximide;

2,4-dichloro-6- o-chloroaniline) -s-triazine;

bis(4-chlorophenyl)-3-pyridylmethanol;

3,3'-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3,5-

thiodiazine-Z-thione) triphenyltin hydroxide;

l,4-dichloro-2,5-dimethoxy benzene;

triphenyltin acetate;

metal (e.g. iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids (or example, ziram or ferbam);

2,6-dichloro-4-nitroaniline;

tetrachloronitroanisole;

hexachlorobenzene;

hexachlorophene;

methylmercury nitrile;

tetrachloroquinone;

2,3-dichloro-1,4-naphthoquinone;

cupric hydroxide;

tribasic copper sulfate;

fixed copper;

sulfur;

1,2-dibromo-3-chloropropene;

1,2-dibromo-3-chloropropane;

dichloropropane-dichloropropene mixture;

ethylene dibromide;

chloropicrin;

sodium monomethyl dithiocarbamate (SMDC);

tetrachloroisophthalonitrile;

Streptomycin Kasugamycin or other antibiotics;

2-(2,4,5-trichlorophenoxy)propionic acid;

p-chlorophenoxyacetic acid;

l-napthalene acetamidc; and

N-( l-naphthyl)acetamide.

The agricultural chemicals listed above are merely exemplary of thecompounds which can be mixed with the active compounds and are notintended to any way limit the invention.

The use of pesticides such as those listed above in combination with acompound within the scope of this invention sometimes appears to greatlyenhance the activity of the active compound. In other 'words, anunexpected degree of activity is sometimes seen when another pesticideis used along with the active compound.

The following examples illustrate the activity of the compounds ofFormula I. All parts are parts by weight unless otherwise indicated.

EXAMPLE 3 Percent Methyl l-(trichloromethylthio) 2 benzimidazole- Theabove compounds are blended and hammer-milled, then air-milled until theactive component is substantially all below 5 microns.

The wettable powder thus prepared is added to water at the rate of 500p.p.m. of the active ingredient. This suspension is used to spray, tothe point of run-off, alternate trees in a field planting of apples.Sprays are applied at weekly intervals from Apr. 25 until June 6. FromJune 6 until the end of the season, the sprays are applied at intervalsof two weeks. The remaining trees in the planting are left unsprayed.

In early September all trees are carefully examined. Trees that weresprayed with the compound of this invention are healthy and free of miteinfestation and fungus damage. The fruit on the sprayed trees isunblemished and of good size. The foliage of the unsprayed trees, on theother hand, is heavily infested with the apple scab fungus (Venturiainaequalis) and the powdery mildew fungus (Podosphaem leucotricha). Alsothe leaves of the unsprayed plants are bady infested with European Redmites (Panonychus ulmi). The fruit on the unsprayed trees is spottedwith scab and of small size.

Any of the compounds named in Examples 1 and 2 may be formulated asdescribed in this example and when used as indicated give similarresults.

EXAMPLE 4 The following formulation is prepared by intimately blendingthe following ingredients and micropulvering them until the particlesare substantially all below 20 microns.

Percent Methyl-l-(trichloromethylthio) 2 benzimidazolecarbamate 50.0Oleic acid ester of sodium isethionate 2.0 Sodium lauryl sulfate 1.0

Synthetic fine silica 47.0

The above 50% wettable powder formulation is dispersed in water to givean active ingredient concentration of 3.6 grams per liter of water.Eight uniform apple trees of the same variety are selected for testing.Four of these are sprayed to run-off, which is approximately 2850 litersper hectare, at weekly intervals during the growing season with theabove formulation, and the other four trees are left unsprayed.

By the end of the season the unsprayed trees have developed very highpopulations of orchard mites and are highly infected with apple scab,Venturia inaequalis. Due to the feeding of the mites, the foliage isrusseted and drops permaturely. Also, the untreated trees have poor twiggrowth and small, spotted fruit. The trees sprayed with methyl 1(trichloromethylthio)-2-benzimidazolecarbamate are essentially free ofmites, their eggs and apple scab. As a result of the excellent mitecontrol, the sprayed trees have foliage of a thrifty, dark green color,and they exhibit good twig growth and fruit size.

EXAMPLE 5 attrition mill until the particle size is substantially lessthan 5 microns and then reblending.

Percent Sec butyl 1 (trichloromethylthio)-2=benzimadozolecarbamate 85.0Alkylnaphthalene sulfonic acid, sodium salt 1.5 Sodium N-methyl-N-oleoyltaurate 2.0 Synthetic fine silica 11.5

Four similar potted bean plants (one plant per pot) are selected. Thesoil in two of these pots is drenched with a water suspension of thewettable powder formulation described above at a rate to provide 30parts per million by weight in the total amount of soil in the pot. Theremaining two pots are left untreated.

Five days after treatment 50 adult mites (Tetranychus telarius) areplaced on a terminal leaf on each of the test plants. Twenty-four hourslater these adult mites, all still alive, are transferred to untreatedbean foliage. After another twenty-four hours all of the adult mites areremoved in a way which causes no damage to the eggs that have been laidduring the twenty-four hour period on the untreated foliage.

A suflicient time is allowed for all viable eggs to hatch. Countsdemonstrate that few of the eggs hatch from among those laid by mitesthat had fed on foliage from pots with soil containing the compound ofthis invention. Hatch to provide living young was complete, on the otherhand, among eggs laid by mites similar handled except that the plantsproviding sustenance were not in contact with a compound of thisinvention. This experiment demonstrates systemic movement in plants andmite ovicide effect.

EXAMPLE 6 A dust concentrate is prepared as follows:

Percent Methyl l-(trichloromethylthio) 2 benzimidazolecarbamate 50Sucrose (commercial cane sugar) 50 The above ingredients are blended andmilled to a particle size below 10 microns, followed by reblend'ing.

A dilute dust is then prepared by blending 16 parts of the above mixturewith 84 parts of ground phosphate rock.

A uniform cherry orchard in Michigan is selected for the test. Alternatetrees are dusted every 14 days at the rate of 910 grams per tree withthe above fungicidal dust formulation. The remaining trees are leftunprotected. On September 1 the trees are examined. The trees that hadbeen dusted with the compound of this invention are green and healthy,with all leaves remaining on the tree. At this time the foliage of theunprotected trees is largely discolored due to attack by the leaf spotfungus (Cocomyces hiemalis) and the two-spotted mite (T etranyehustelarius). Further, much of the foliage of the unprotected trees hasfallen due to the effect of the two pests.

EXAMPLE 7 The following ingredients are converted into a dust asindicated:

Percent Sec butyl l (trichloromethylthio)-2-benzimidazolecarbamate 20Pyrophyllite 79 Alkylnaphthalene sulfonic acid, sodium salt 1 Equalparts of the active ingredient and the diluent are milled with thesurfactant and then diluted with the remaining pyrophyllite in a ribbonblender. The components are then blended until they are homogeneous.

Cotton plants in selected plots are thoroughly dusted at a rate of 10kilograms of dust per hectare for each application on June 20 and attwo-week intervals thereafter until mid-August with the above dustformulation in addition to a regular insecticidal program. Similar plotsreceive the insecticidal application only. By late August the plotsreceiving the insecticide only have a high incidence of boll rot causedby Aspergillus niger and high populations of spider mites, Tetranychusspp., which cause the leaves of the cotton plants to turn rusty brown,twist and drop to the ground. Many bolls are completely rotted and lossof leaves results in the shedding of small bolls and prevents the lintfrom becoming fully developed. Cotton plants treated with the above dustformulation retain healthy foliage and produce a heavy crop of healthyfull-sized bolls.

EXAMPLE 8 A granular formulation is prepared as follows:

Percent Granular corn cob (15-30 mesh, i.e. approx. 0.59-

Methyl l-(trichloromethylthio) 2 benzimidazolecarbamate 10 The activecompound is dissolved in Warm chloroform and the chloroform solution issprayed on the granular corn cob which is being tumbled in a mixer.Evaporation of the chloroform yields a finished granule in which theactive ingredient is absorbed.

A field in California is seeded with cotton in the normal manner, exceptthat granules prepared as set forth above are added to alternate rows.These granules are dropped in such a way that some fall into the furrowand some are mixed with the covering soil. The rate of granuleapplication is such as to employ 0.45 kilogram of active chemical ofthis invention per 3,600 meter of row. The remaining rows are untreated.

Six weeks after planting, many of the plants in the rows without thegranules are dead, and others show soreshin lesions caused byRhizoctonia solani as well as heavy populations of the Pacific mite(Tetranychus pacificus). In the rows that had received the granules, allplants remain alive and are healthy, and further they are free of mites.The effect on mites is clearly systemic.

EXAMPLE 9 A wettable powder formulation is prepared from the followingingredients in the proportions given:

Percent Methyl l (trichloromethylthio) 2 benzimidazolecarbamate 25Methyl O-(methylcarbamyl)thiolacetohydroxamate l Oleic acid ester ofsodium isethionate 2 Sodium lauryl sulfate 2 Diatomaceous silica 61 Allingredients are combined and rotated in a blender until uniformlyadmixed. The total mix is then air-milled to produce particles most ofwhich are less than microns in particle size.

A sufficient amount of the above wettable powder is added to water suchthat there are 2.5 grams per liter of water of the methyl 0(methylcarbamoyl)thioaceto hydroxamate. The resulting suspension is thensprayed at weekly intervals on one of a pair of similar, adjacent plotsin a greenbean field in Florida at the rate of two kilograms of methyl 1(trichloromethylthio) 2 benzimidazolecarbamate per hectare. The testarea is selected as one in which there is a high infestation of thetwospotted mite, Tetranychus bimaculatus, and the Mexican bean beetle.Epilachna varivestis. The plot sprayed with the above formulationremains free of both the twospotted mite and the Mexican bean beetle forthe entire growing season and provides a good yield of greenbeans. Theunsprayed plot is attacked by both of the above pests and is damaged tothe extent that the yield is greatly reduced. Similar areas sprayed withmethyl O-(methylcarbamyl)thiolacetohyroxamate alone are free from attackby the Mexican bean beetle but are damaged by the two-spotted mite.

In theabove example methyl O-(carbamyl)thiolaceto- 18 hydroxamate or Smethyl 1 dimethylcarbamoyl N- [(methylcarbamoyl)oxy]thioformimidate maybe substituted for methyl O-(methylcarbamyl)thiolacetohydroxamate withessentially equivalent results.

EXAMPLE 10 A wettable powder formulation is prepared from the followingingredients in the proportions given:

Percent Methyl l-(trichloromethylthio) 2 benzimidazolecarbamate 30.0Methoxychlor 30.0 Sodium lauryl sulfate 1.0 Oleic acid ester of sodiumisethionate 2.0

Non-swelling montmorillonite clay 37.0

All of the ingredients are combined and rotated in a blender untiluniformly mixed. The total mix is then airmilled to produce particlesessentially less than 40 microns 1n size.

The wettable powder prepared above is added to water in an amount suchthat there are 2.5 grams of each of the active ingredients per liter ofwater. The resulting suspension is sprayed at the rate of 10 kilogramsper hectare for each of the active ingredients over a plot in aBermudagrass turf area in Florida. The area selected for the test isheavily infested with a plant-feeding mite, Aceria neocynodomis, andchinch bugs, Blissus leucopterus insularis. The chinch bugs are killedin the treated plot and the mite infestation soon disappears. The turfquickly returns to a healthy and attractive condition.

In a similar untreated plot both the mites and the chinch bugs continueto multiply and, by their feeding, the Bermudagrass becomes discloredand the turf reflects many unsightly dead spots. Similar plots sprayedwith methoxychlor only are free of damage due to chinch bugs but areinjured by the high mite infestation.

EXAMPLE 11 Percent Methyl l-(trichloromethylthio) 2benzimidazolecarbamate 30.0 Thirarn 30.0 Dioctyl sodium sulfosuccinate(Aerosol OTB) 3.0 Low viscosity methyl cellulose (MethoceP 15) 0.5Carbon black 1.0 Sucrose (commercial cane sugar) 35.5

The ingredients are blended and the mixture is first hammer-milled, thenair-milled twice, until the active ingredient is present in particlessubstantially all of which are smaller than 5 microns.

The mixture of fungicides described above is diluted in a spray tank toa concentration of 1,000 p.p.m. of combined active ingredients. It issprayed to run off on apple trees in a portion of an orchard every twoweeks during the growing season. At harvest, the treated trees arehealthy and producing an abundance of normal fruit. The untreated trees,on the other hand, are partly defoliated by apple scab (Ventu'riainaequalis), cedar apple rust (Gymosporangium juniperivirginianae) andpowdery mildew (Podosphaera leucotricha). The fruit on the untreatedtrees is scabby, distorted with rust lesions and unmarketable due to theattack of these fungus pathogens. The degree of protection from thiscomplex of serious diseases by the treatments with the above mixture isoutstanding.

EXAMPLE 12 A wettable powder is prepared by the methods shown in Example3:

A wettable powder is prepared by blending and hammer-milling thefollowing ingredients:

Percent Maneb 60 Alkylnaphthalene sulfonate, sodium salt (Alkanol B)Polyvinylpyrrolidone derivative (Ganex 904) 1 Cane Sugar 34 Equalportions of these two powders are combined, blended, and hammer-milledto produce a powder containing 30% each of the two fungicides.

The wettable powder is suspended in water at a rate to obtain 1000p.p.m. of the combined active ingredients. This mixture is sprayed torun-oil on a single row of grape vines on a weekly schedule during thegrowing season. At harvest the treated vines and grapes are healthy andproducing an abundance of normal fruit. The untreated plants in adjacentrows, on the other hand, are severely injured by downy mildew incited byPlasmopara viticola, powdery mildew incited by Uncinula necator and graymold incited by Bo'trytis cinerea.

EXAMPLE 13 Percent Methyll-(2,4-dinitrophenylthio)-2-benzimidaz0lecarbamate 60 Dioctyl sodiumsulfosuccinate 3 Low viscosity methylcellulose 0.5 Sulfur (sublimed)36.5

The above composition is blended, hammer-milled, and air-milled in thesame manner as previous examples.

Test plots are established in a rice field. The plots are sprayed withwater containing a suspension of the wettable powder described abovealong with a polyhydric alcohol ester surface active agent (Trem 014).The amount of the wettable powder used is such as to provide 1.5 gramsof the active compound of this invention per liter of water. The amountof Trem 014 is 400 ppm. in the final spray. The spray is applied atWeekly intervals at the rate of 900 liters per hectare. The remainder ofthe field is left unsprayed. Three months after the start of the test,the sprayed plots are healthy and growing well. The untreated plots onthe other hand, are seriously damaged by the rice blast fungus,Piriculariw oryzae which greatly reduces yield.

EXAMPLE 14 A dust formulation is prepared from the following ingredientsin the proportions listed:

Percent sec-Butyl 1-(trichloromethylthio)R-2- benzimidazolecarbamate 5Methoxychlor 5 Sodium alkylnaphthalenesulfate 1 Pyrophyllite clay 89 Ris methyl, ethyl, isopropyl or sec-butyl; and Z is alkyl of 1 through 3carbon atoms; alkyl of 1 through 3 carbon atoms substituted withchlorine; phenyl; phenyl substituted with methyl, nitro, or chlorine;benzyl; or

benzyl substituted with methyl, nitro or chlorine. 2. A compound of theformula:

R is methyl, ethyl or isopropyl; and Z is trichloromethyl or2,4-dinitrophenyl.

3. Methyl 1 (trichloromethylthio) 2 benzimidazolecarbamate.

4. Ethyl 1 (trichloromethylthio) 2 benzimidazolecarbamate.

5. Methyl 1-(2,4-dinitrophenylthio)-2-benzimidazolecarbamate.

6. Ethyl 1 (2,4-initrophenylthio)-2-benzimidazolecarbamate.

wherein wherein References Cited UNITED STATES PATENTS 2,933,502 4/ 1960Klopping 260-3092 2,933,504 4/ 1960 Klopping 260-3092 3,010,968 11/1961Loux 260-3092 3,369,027 2/1968 Klauke et a1. 260-3092 FOREIGN PATENTS666,795 1/1966 Belgium 260-3092 OTHER REFERENCES Ridi et a1.: Chem.Abst., V01. 49, columns 4658-9 (1955), QDLASl.

NATALE TROUSOF, Primary Examiner US. 01. X.R. 424-273

